Process for breaking petroleum emulsions



Patented Feb. 14, I933 UNITED STATES PATENT OFFICE MELVIN DE GROOTE, OFST. LOUIS,

LOUIS T. MONSON, OF MAPLEWOOD, AND ARTHUR F. WIRTEL, OF WEBSTER GROVES,MISSOURI, ASSIGNORS, BY MESNE ASSIGNMENTS, TO TRETOLITE COMPANY, OFWEBSTER GROVES, MISSOURI, A CORPORATION OF MISSOURI PROCESS FOR BREAKINGPETROLEUM EMULSIONS No Drawing.

producing wells and from the bottoms of oil storage tanks and arecommonly referred to as cut oil, roily oil, emulsified oil and bottomsett-lings.

The object of our invention is to provide a novel and inexpensiveprocess for separating emulsions of the character referred to into theircomponent parts of oil and water or brine.

Briefly described, our process consists in subjecting a petroleumemulsion of the waterin-oil type to the action of a treating agent ordemulsifyin g agent of the kind hereinafter described, thereby causingthe emulsion to break down and separate into its component parts of oiland water or brine, when the emulsion is permitted to remain in aquiescent state after treatment.

The treating agent or demulsifying agent used in our process is asubstituted aromatic sulfonic' body of the type XR-R SO Z, where- 'in Xstands for a bicyclic aromatic nucleus and BB stands for more than onealcohol residue derived from an alcohol or alcohols having fewer thantwelve carbon atoms in the molecule, S0 is the sulfonic residue, and Zis an hydrogen ion equivalent of the kind subsequently defined, saidtreating agent being also characterized by the fact that inconcentrations of not over 1%, it will produce a precipitate whendiluted with an excess of an aqueous solution of alkaline earth salts.

The treating agent or demulsifying agent above described is produced orobtained by introducing alcohol residues having fewer than twelve carbonatoms each, into a bicyclic nucleus. Instead of the unaltered bicyclicaromatics, derivatives may be employed, such as halogen derivatives,nit-r0 derivatives, hy-

Application filed January 21, 1929. Serial No. 334,106.

droxy derivatives, or hydrogenated deriva tives. If desired, thesulfonic group may be introduced into the bicyclic body before theintroduction of an alcohol residue of the kind described; for instance,naphthalene sul fonic acid or naphthalene disulfonic acid or betanaphthol sulfonic acid may be employed.

In manufacturing said treating agent alco-" hol residues of the kinddescribed can be introduced into the aromatic nucleus by threewell-known methods. One method depends on the fact that these alcoholscan be condensed with bicyclie aromatics by treating them with strongsulfonating agents, such as sulfuric acid, oleum, or chloro-sulfonicacid, preferably in excess at elevated temperatures, and especially inthe presence of a small quantity of a phosphorus compound, such asphosphoric acid, phosphorus pentachloride, or phosphorus oxychloride.During such condensing operation sulfonation of the aromatic body alsotakes place, thus producing a sulfonated substituted aromatic.Obviously, more than two alcohol residues can be introduced into abicyclic body, and furthermore more than one sulfonic group can beintroduced.' It is not necessary that a single alcohol body be used, buttwo or more different alcohols may be employed; for instance, methylalcohol, ethyl alcohol, and butyl alcohol.

It should be understood that the above reaction is not limited to theintroduction of residues from aliphatic alcohols, but can also beapplied to the introduction of a residue from an aromatic alcohol suchas hexahydrophenol. Likewise, aralkyl alcohols may be employed, such asbenzyl alcohol, or a cyclic alcohol may be employed, such ascyclobutanol. In the introduction of two or more alcohols, as noted,they need not be of the same kind; for instance, one may be an alkylalcohol, such as propyl alcohol, and the other may be an aromaticalcohol, such as hexahydropheno or else one may be an aralkyl alcohol,sucli sfizbenzyl alcohol and the other may be a cycl lcohol such ascyclobutanol.

Another method of producing the treating agent used in our process is toemploy the well-known F riedel and Crafts reaction for introducing asubstitution residue into an aromatic. Methyl alcohol may be convertedby action of a suitable phosphorus halogen compound into a suitablemethyl halide such as methyl chloride. This material can be treated witha bicyclic aromatic of the kind above described in the presence ofanhydrous aluminum chloride to give the substituted aromatic. Saidaromatic can be subsequently sulfonated to give a substituted aromaticsulfonic body of the kind described in the preceding procedure. Thissecond procedure, namely, that of Friedel and Craft, will not bedescribed further, because it is possibly the best known reaction ofaromatic chemistry.

Still another method that may be used to produce our treating agent isto dissolve the aromatic such as naphthalene or tetralin in an excess ofsulfuric acid or other suitable sulfonating agent and pass into same amaterial such as ethylene, propylene, butylerre, or amylene.

WVhile various procedures may be used to produce the material that isemployed as the treating agent of our process, we prefer to produce saidmaterial by complete reaction of two moles of propyl alcohol and onemole o' amyl alcohol and one mole of naphthalene in the presence of alarge excess of 66 sulfuric acid preferably at a temperature above themelting point of naphthalene. Said reaction is continued until at leasttwo and preferably three alcohol groups are introduced into the bicyclicnucleus with a simultaneous inti oduction of one sulfonic group. Thereaction involving the introduction of the sulfonic group, of course, iswell understood. The introduction of the propyl-groups and'the amylgroup depends on the formation of propyl (or amyl) acid sulfate with thesplitting out of water. Said propyl (or amyl) acid sulfate,underconditions described, re-

acts with the bicyclic body to yieldthetdesired material. Whensulfonation is complete, the mass is diluted with water until an upperlayer separates. The upper layer is drawn off and neutralized with anysuitable base such as caustic soda, caustic potash, or ammonia. Weprefer to 'use ammonia. The material produced by the above procedure istested for the production of insoluble alkaline earth salts. Forexample, a 1% solution of said material may be mixed with a 1% solutionof magnesium sulfate, and heated for 10 to 30 minutes in a water bathjust below the boiling; point of water, if required. In the test witheither the calcium salt or the magnesium salt, a precipitate should beobtained which remains after the mixture is diluted with two times itsvolume of distilled water...

There is no objection to an excess of alkali if desired. The materialcan also be converted into an ester by esterification in the usualmanner to produce an aromatic or aliphatic ester such as the ethylester. Some of the esters so produced may be oil-soluble, such as thehexyl ester.

As indicated, the said material may be acidic in nature, and the complexsubstituted aromatic sulfonic group may be united with an acid hydrogenion, as is the case when the acid itself is employed. hen said acidicmaterial is neutralized, the hydrogen ion is replaced by a suitablemetallic ion or its equivalent, such as a true metallic ion or anammonium radical. In the event that said material is esterified, thehydrogen ion is replaced by an organic radical such as an ethyl radical.lVe will refer to the hydrogen ion or its metallic substitute or itsorganic substitute as the hydrogen ion equivalent.

Materialof the kind above described can be used as a demulsifyingagentin an anhydrous state or in solutions of any convenient strength. Aconcentrated solution of said *material can be emulsified into oil byagency of any suitable oil-soluble emulsifier such as calcium oleate andused in this condition to treat the emulsion. Said material can be usedalone to form the demulsifying agent of our process or it can becombined with other wellknown treating agents for petroleum emulsions ofthe water-in-oil type, such as water softeners, modified fatty bodies ortheir soaps, petroleum sulfonic acids or their soaps, or othersubstances having similar properties.

In manufacturing or producing the treating agent employed in ourprocess, we contemplate using only substances of the above class thatyield insoluble precipitates with either soluble calcium or solublemagnesium salts, and we contemplate using only alcohols having fewerthan twelve carbon atoms.

In practising our process, a treating agent or demulsifying agent of thekind above. described may be brought in contact with the emulsion to betreated in any of the numerousways now employed in the treatment ofpetroleum emulsions of the water-in-oil type with chemical demulsifyingagents, such, for example, as by introducing the treating agent into thewell in which the emulsion is produced, introducing the treating agentinto a conduit through which the emulsion is flowing, introducing thetreating agent into a tank in which the emulsion is st red, orintroducing the treating agent int a container that holds a sludgeobtained from the bottom of an old storage tank. In some instances, itmay be advisable to introduce the treating agent into a producing wellin such a way that it will become mixed with water and oil that areemerging from the surrounding 2. UUIVHUSIHUNS,

strata, before said water and oil enter the barrel of the well pump orthe tubing up through which said water and oil flow to the surface ofthe ground.

After treatment the emulsion is allowed to stand in a quiescent state,usually in a settling tank, at a temperature varying from atmospherictemperature to about 200 F., so as to permit the water or brine toseparate from the oil, it being preferable to keep the temperature lowenough so as to prevent the valuable constituents of the oil fromvolatilizing'. If desired, the treated emulsion may be acted upon by oneor the other of various kinds of apparatus now used in the operation ofbreaking petroleum emulsions, such as homogenizers, hay tanks, gunbarrels, filters, centrifuges or electrical dehydrators.

The amount of treating agent on the anhydrous basis that is required tobreak the emu]- sion may vary from approximately 1 part of treatingagent to 500 parts of emulsion, up to a ratio of 1 part of treatingagent to 20,000 parts of emulsion, depending upon the type or kind ofemulsion being treated. In treating exceptionally refractory emulsionsof the kind commonly referred to as tank bottoms or residual pit oils,the minimum ratio not fewer than two alcohol residues derived fromalcohols having fewer than twelve carbon atoms each; S0 represents theconventional sulfonic acid residue; and Z represents an hydrogen ionequivalent, said demulsifying agent being also characterized by the factthat in concentrations of not over 1%, it will produce a precipitatewhen diluted when an excess of an aqueous solution of alkaline earthsalts.

3f A process for breaking a petroleum emulsion of the water-in-oil type,which consists in subjecting the emulsion to the action of ademulsifying agent containing a watersoluble substituted bicyclicaromatic sulfonic body of the type Xltl-tfsO Z; wherein X 'is a bicyclicaromatic nucleus; RR represents not fewer than two alcohol residuesderived from alcohols having fewer than 12 carbon atoms each; S0represents the conventional sulfonic acid residue, and Z represents ametallic ion equivalent, said demulsifying agent being alsocharacterized by the fact that in concentrations of not over 1%, it willproduce a precipitate when diluted with an excess of an aqeous solutionof alkaline earth salts. K V

4. A process for breaking a petroleum above referred to is often necessay, but emulsion of the water-in-Dil type which contreating freshemulsions, i. e., emulsions that will yield readiv to the action ofchemical demulsifying agents, the maximum ratio above mentioned willfrequently produce highly satisfactory results. For the averagepetroleum emulsion of the water-in-oil type a ratio of 1 part oftreating agent to 5,000 parts of emulsion will usually be found toproduce commercially satisfactory re ults.

Having thus described our invention, what we claim as new and desire tosecure by Letters Patent is:

1. A process for breaking a petroleum emulsion of the water-in-oil type,which conssts in subjecting the emulsion to the action of a demulsifyingagent containing a substituted bicyclic aromatic sulfonic body of thetype XRR SO Z, wherein X is a bicyclic aromatic nucleus; BB representsnot fewer than two alcohol residues derived from-{1cohols having fewerthan twelve carbon atoms each; SO represents the conventional sulfonicacid residue; and Z represents an hydrogen ion equivalent, saiddemulsifying agentbeing also characterized by the fact that inconcentrations of not over 1%, it will produce a precipitate whendiluted with an excess of an aqueous solution of alkaline earth salts.

2. A process for breaking a petroleum emulsion of the water-in-oil type,which consists in subjecting the emulsion to the action of ademulsifying agent containing a watersoluble substituted bicyclicaromatic sulfonic body of the type XRR SO Z, wherein X is a bicyclicaromatic nucleus; R11 represents sists in subjecting the emulsion to theaction of a demulsifying agent containing a watersoluble substitutedbicyclic aromatic sulfonic body of the type XRR SO Z; wherein X is abicyclic aromatic nucleus; RR represents not fewer than two alcoholresidues derived from alcohols having fewer than twelve carbon atomseach; S0 represents the convehta dnal sulfonic acid residue; and Zrepresents an ammonium radical, said demulsifying agent being alsocharacterized by the fact that in concentrations of not over 1% it willproduce a recipitate when diluted with an an excess of an aqeoussolution of a1- kaline ear salts.

5. A process for breaking a petroleum emulsion of the water-in-oil type,which consists in subjecting the emulsion to the action of ademulsifying agent containing a substituted bicyclic aromatic sulfonicbody of e type XRR SO Z, wherein X is a bicy aromatic nucleus; RRrepresents two alcohol residues derived from7alcohols having fewer thantwelve carbon atoms each; SO represents the conventional sulfonic acidresidue, and Z represents an hydrogen ion equivalent, said demulsifyingagent being also characterized by the fact that in concentrations of notover 1%, it will produce a precipitate when diluted with an excess of anaqueous solution of alkaline earth salts.

6. A process for breaking a petroleum emulsion of the water-in-oil type,which consists in subjecting the emulsion to the action of ademulsifying agent containing a watersoluble substituted bicyclicaromatic sulfonic body oi the type XRRSQ Z, wherein X is a bicyclicaromatic nucleus; RR represents two alcohol residues derived fromalcohols having fewer than twelve carbon atoms each; SO represents theconventional snltonic acid residue, and Z represents an hydrogen ionequivalent, said leinull' ving agent being also characterized by thefact that in concentrations of not over lfi, it will produce aprecipitate when diluted with an excess of an aqueous solution ofalkaline earth salts.

7. A process for breaking a petroleum emulsion of the water-in-oil type,which consists in subjecting the emulsion to the action of adcmulsii'yin y agent containing a water soluble substituted b'xeyclicaromatic sultonic body of the type XllllF-O -Z, wherein X is a bicyclicaromatic nucleus: RIP represents two alcohol residues derived fromalcohols having fewer than twelve carbon atoms each: 50,-, representsthe conventional sultonic acid residue, and Z represents a n'ietallicion equivalent, said demulsit ving agent being also characterized by thefact that in concentrations of not over 17}, it. ,will produce aprecipitate when diluted with an excess of an aqueous solution ofalkaline earth salts.

8. A process for breaking a petroleum emulsion of the water-in-oil type,which dmsists in subjecting the emulsion to the action of a demnlsityingagent containinga watersoluble substituted bicyclic aromatic body of thetype XRR SQZ; wherein X is a bicyclic aromatic nucleus: RR representstwo alcohol residues derived from alcohols having fewer than twelvecarbon atoms each: S03 represents the conventional sult'onic acid resisdue, and Z represents an ammonium radical. said demulsitying agent beingalso characterized by the tact that in concentrations of not over 1%, itwill produce a precipitate when diluted with an excess of an aqueoussolution of alkaline earth salts.

9. A process for breaking a petroleum emulsion of the water-inoil type,which consists in subjecting the emulsion to the action of ademulsifying agent containing a substituted bicyclic aromatic sulfoniebody of the type XRR sO Zg wherein X is a bicyclic aromatic nucleus: R11 represents two dissimilar alcohol residues derived from alcoholshaving fewer than twelve carbon atoms each; S03 represents theconventional sulfonic acid residue, and Z represents an hydrogen ionequivalent, said dcmulsitying agent being also characterized by the tactthat in com-entrations of not over 1)? it will produce a precipitatewhen diluted with an excess of an aqueous solution of alkaline earthsalts.

10, A process for breaking a petroleum emulsion of the water-in-oi type.which conin subjecting the emulsion to the action of a demulsifyingagent containing a watersoluble substituted bicyclic aromatic snltonicbody of the type XRIPSO Z, wherein .X

is a bicyclic aromatic nucleus; RR represents two dissimilar alcoholresidues derived from alcohols having fewer than twelve carbon atomseach; S0 represents the conventional sulfonic acid residue, andZ'represents an hydrogen ion equivalent, said demulsifying agent beingalso characterized by the fact that in concentrations of not over 1%, itwill produce a precipitate when diluted with an excess of an aqueoussolution of alkaline earth salts.

11. A process for breaking a petroleum emulsion of the water-in-oiltype, which consists in subjecting the emulsion to the action ofademulsitying agent containing a watersoluble substituted bicyclicaromatic sulfon ic. body of the type XRR CO Z; wherein X is a bicyclicaromatic nucleus; RR represents two dissimilar alcohol residues derivedfrom alcohols having fewer than twelve carbon atoms each; SQ,represcnt-- the conventional sulfonic acid residue, and Z represents ametallic ion equivalent, said demulsifying agent being alsocharacterized by the fact that in concentrations of not over 1%, it willproduce a precipitate when diluted with an excess of an aqueous solutionof alkaline earth salts.

12. A process for breaking a petroleum emulsion of the water-in-oiltype, which consists in subjecting the emulsion to the action of ademulsifying agent containing a watersoluble substituted bicyclicaromatic sultonic body of the type XRR SO Z; wherein X is a bicyclicaromatic nucleus; RR represents two dissimilar alcoholresidues derivedfrom alcohols having 'fewer than twelve carbon atoms each; S0 representsthe conventional sulfonic' acid residue, and Z represents an ammoniumradical, said demulsifying agent being also characterized by the factthat in concentrations of not over 1%, it will produce a precipitatewhen diluted with an excess of an aqueous solution of alkaline earthsalts.

13. A process for breaking a petroleum emulsion of the water-in-oiltype, which consists in subjecting the emulsion to the action of ademulsifying agent containing a substituted bicyclic aromatic sulfonicbody of the type XRR SO Z, wherein X is a bicyclic aromatic nucleus; BBrepresents two dissimilar alcohol residues, at least one of which is analiphatic alcohol residue, derived from alcohols having fewer thantwelve carbon atoms each; SO represents the conventional snlfonic acidresidue, and Z represents an hydrogen ion equivalent, said demulsityingagent being also characterized by the fact that in concentrations of notover 1%, it will produce a precipitate when diluted with an excesis ofan aqueous s vlution of alkaline earth sa ts.

14-. A process for breaking a petroleum emulsion of the water-in-oiltype, which consists in subjecting the emulsion to the action 252.COMPOSITIONS,

of a demulsifying agent containing a watersoluble substituted bicyclicaromatic sulfonic body of the type XRR SO Z, wherein X is a bicyclicaromatic nucleus RR- represents two dissimilar alcohol residues, atleast one of which is an aliphatic alcohol residue derived from alcoholshaving fewer than twelve carbon atoms each; S0 represents theconventional sulfonic acid residue, and Z represents an hydrogen ionequivalent, said treating agent being'also characterized by the factthat in concentrations of not over 1%, it will produce a precipitatewhen diluted with an excess of an aqueous solution of alkaline earthsalts.

15. A process for breaking a petroleum emulsion of the water-in-oiltype, which consists in subjecting the emulsion to the action of ademulsifying agent containing a watersoluble substituted bicyclicaromatic sulfonic body of the type XRR SO gZ; wherein X is a bicyclicaromatic nucleus; BB represents two dissimilar alcohol residues, atleast one of which is an aliphatic alcohol residue, derived fromalcohols having fewer than twelve carbon atoms each; S0 represents theconventional sulfonic acid residue, and Z represents a metallic ionequivalent, said demulsifying agent being also characterized by the factthat in concentrations of not over 1%,it will produce a precipitate whendiluted with an e cess of an aqueous solution of alkaline earth salts. y

16. A process for breaking a .petroleum emulsion of the water-in-oiltype, which consists in subjecting the emulsion to the action of ademulsifying agent containing a watersoluble substituted bicyclicaromatic sulfonic body of the type XRR SO Z. wherein X is a bicyclicaromatic nucleus; EH represents two dissimilar alcohol residues, atleast one of which is an aliphatic alcohol residue, derived fromalcohols having fewer than twelve carbon atoms each; S03 represents theconventional sulfonic acid residue, and Z represents an ammoniumradical, said demulsifying agent being also characterized by the factthat in concentrations of not over 1%, it will produce a precipitatewhen diluted with an excess of an aqueous solution of alkaline earthsalts.

17. A process for breaking a petroleum emulsion of the water-in-oiltype, which consists inpubjecting the emulsion to the action of adeinulsifving agent containing a substituted bicvclic aromatic sulfonicbody of the type XRR SO Z; wherein X is abicyclic aromatic body RRrepresents two dissimilar aliphatic alcohol residues. of which at leastone is a propyl alcohol residue. derived from alcohols having fewer thantwelve carbon atoms each; SO, represents the conventional sulfonic acidresidue. and Z represents an t me that in concentrations of not over 1%,it will produce a precipitate when diluted with an excess of an aqueoussolution of alkaline earth salts.

18. A process for breaking a petroleum emulsion of the water-in-oiltype, which consists in subjecting the emulsion to the action of ademulsifying agent containing a watersoluble substituted bicyclicaromatic sulfonic body of the type XRIPSQZ, wherein X is a bicyclicaromatic nucleus; RR represents two dissimilar aliphatic alcoholresidues, of which at least one is a propyl alcohol residue. derivedfrom alcohols having fewer than twelve carbon atoms each; S0 representsthe conventional sulfonic acid residue, and Z represents an hydrogen ionequivalent, said demulsifying agent being also characterized by factthat in concentrations of not over 1%, it will produce a precipitatewhen (lillIU-(l with an excess of an aqueous solution of alkaline earthsalts.

10. A process for breaking apetroleum emulsion of the water-in-oil type,which consists in subjecting the emulsion to the action of ademulsifying agent containing a watersoluble substituted bicyclicaromatic sulfonic body of the type XRRHSO Z; wherein X is a bicyclicaromatic nucleus; RB represents two dissimilar aliphatic alcoholresidues, of which at least one is a propyl alcohol residue, derivedfrom alcohols having fewer than twelve carbon atoms each; so, representsthe con ventional sulfonic acid residue, an Z represents a metallic ionequivalent, sai demulsifying agent being also characterized by the factthat in concentrations of not over 1%, it will produce a precipitatewhen diluted with an excess of an aqueous solution of alkaline earthsalts.

.20. A process for breaking a petroleum emulsion of the water-in-oiltype, which consists in subjecting the emulsion to the action of ademulsifying agent containing a watersoluble substituted bicyclicaromatic sulfonic body-of the type XRR SO Z; wherein X is a bicyclicaromatic nucleus, BB represents two dissimilar aliphatic alcoholresidues, of which at least one is a propyl alcohol residue, de-

rived from alcohols having fewer than twelve carbon atoms each; Orepresents the conventional sulfonic acid residue, and Z represents anammonium radical, said demulsifying agent being also characterized bythe fact that in concentrations of not over 1%, it will produce aprecipitate when diluted with an excess of an aqueous solution ofalkaline earth salts.

MELVIN DE GROOTE.

LOUIS T. MONSON.

ARTHUR F. W'IRTEL.

hydrogen ion equivalent. said demulsifying agent being alsocharacterized by the fact GERTIFECATE 0F CORRECTION.

neat Ns. 1, 89?, 575.

MELVEN DE GRGSTEB, ET AL.

It is hereby certified that ermr apps-are in the primeii specificationof the ab've numbeniii patent requiring cmfr'eeiiozs as feilaws:

Fage 3 fine 74,

ciaim for "vi=ex1"'read; "M121"; and that the sai Letters Patent shouldbe read with this correction therein thai the same may cunfarm to thereccar of the case in the Patent Office.

Signed am sealed this 9th day cf May, A. D. i933.

M. J. Meme. (Seal) Acting Gemmissioner of Patents,

February 14, 1933.

